1,3-bis-(nitroalkyl) 5,5-di-nitrohexahydro pyrimidines



This invention relates to new compositions of matter and a method for their preparation. In particular this invention relates to polynitro-1,3-diazines having the general formula:

wherein A is an alkylene radical and R is a nitro or alkyl radical.

This application is a continuation in part of my copending United States patent application Serial No. 419,618 filed March 29, 1954, and now abandoned.

The compositions of this invention are useful as high explosives and can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge. An example of such a missile is disclosed in United States Patent No. 2,470,162, issued May 17, 1949. One way of using the high explosives of this invention in a device such as that disclosed in United States Patent No. 2,470,162, is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufliciently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impactor time fuse-mechanism firing a detonating explosive such as lead azide or mercury fulminate.

The compounds of this invention are readily prepared by the condensation of nitro-containing secondary amines with formaldehyde, in accordance with the general reaciton scheme set forth below:

wherein A and R are as defined above.

The secondary amines used as starting materials in this invention are prepared by condensing a primary amine with 2,2-dinitro-1,3-propanediol, as disclosed in assignees copending application No. 419,615, filed March 29, 1954, and now abandoned.

The primary amines are prepared by the method disclosed in assignees copending application No. 405,515, filed January 21, 1954, now US 2,923,726.

To more clearly illustrate this invention, the following examples are presented. It is to be understood, however, that these examples are presented merely as a means of illustration and are not intended to limit the scope of the invention in any way.

EXAMPLE I Preparation of 1,3-bis(3',3',3-trinitr0pr0pyl)-5,5-dinitr0- hexahydro-I ,3 -diazine In a flask, fitted with a mechanical stirrer, was placed 12.4 gm. (0.075 mole) of 2,2-dinitro-1,3-propanediol, 34.5 gm. (0.15 mole) of 3,3,3-trinitropropyl amine hydrochloride, and ml. of water. To this solution was added dropwise 30.7 ml. of 4.8777 N sodium hydroxide solution (0.15 mole). After stirring [for 15 minutes a yellow solid had separated. The water was decanted and the product was water-washed by decantation. The solid was dissolved in 200 ml. of hot methanol, cooled to 30 C., and 12.1 gm. (0.15 mole) of 37% formalin was added. The reaction mixture was stirred for 1 hour; at this time 16.2 gm. (40.8%) of light yellow solid had separated. Evaporation of the methanol solution gave a trace of brown solid. Recrystallization of the product from chloroform yielded yellow rods, M.P. 119-121 C. dec., exhibiting an impact stability of 5 to 10 cm./2 kg. The elemental analysis of the product is as follows:

Calculated for C H N O Percent C, 22.65; percent H, 2.66; percent N, 26.42. Found: percent C, 22.95; percent H, 2.65; percent N, 26.72.

The explosive power is as follows:

Lead block value 153 T.N.T.=l00 Ballistic mortar value 157 T.N.T.=

EXAMPLE II Preparation of 1,3-bis(3',3'-dinitrobutyl)-5,5-dinitrohexahydro-1,3-diazine A 9.1 gm. quantity (0.02 mole) of 2,2,7,7,12,l2-hexanitro-5,9-diazatridecane, 1.62 gm. (0.02 mole) of 37% formalin, and ml. of methanol was placed in a. 300 ml. 3-necked flask, fitted with a sealed mechanical stirrer and reflux condenser. The reaction mixture was heated on a steam bath for 1 hour at which time most of the solid had dissolved. On cooling 5.5 gm. (58.8%) of white solid separated. Two recrystallizations from methanol yielded a product, M.P. 127-127.5 C. (dec.), exhibiting an impact stability greater than 100 cm./ 2 kg. The elemental analysis of the product is as follows:

Calculated for C H N O Percent C, 30.77; percent H, 4.31; percent N, 23.93. Found: Percent C, 30.80; percent H, 4.44; percent N, 23.98.

I have also found that the condensation products of 2,2-dinitro-1,3-propanediol with such amines as 4,4,4- trinitrobutyl amine, 3,3-dinitropentyl amine, and 4,4- dinitropentyl amine, will also react with formaldehyde to form corresponding diazines; namely, 1,3-bis(4',4',4'- trinitrobutyD-S ,5 -dinitrohexahydro-1,3-diazine, 1,3 bis- (3',3'-dinitropentyl) 5,5 dinitrohexahydro-1,3-diazine, and 1,3-bis(4',4'-dinitropentyl)-5,5-dinitrohexahydro-1,3- diazine.

It is apparent from this that any diazine of this series may be prepared by merely condensing the appropriate nitro-substituted amine with formaldehyde, in accordance with the examples given above, to obtain the valuable explosives of this invention.

I claim:

1. As compositions of matter, the N-nitroalkyl-1,3- diazines having the formula:

wherein A is a lower alkylene radical and R is a radical selected from the group consisting of lower alkyl and nitro radicals.

2. As compositions of matter, the N-nitroalkyl-l,3- diazines having the formula:

wherein A is a lower alkylene radical.

3. As compositions of matter, the N-nitroalkyl-1,3- diazines having the formula:

wherein A is a lower alkylene radical and R is a lower alkyl radical.

4. As a composition of matter, 1,3-bis(3',3',3-trinitropropyl)-5,S-dinitrohexahydro-L3-diazine, having the structural formula:

5. As a composition of matter, 1,3-bis(33'-dinitrobutyl)-5,S-dinitrohexahydro-1,3-diazine, having the structural formula:

6. The method of preparing N-nitroalkyl-1,3-diazines having the formula:

which comprises condensing formaldehyde with a polynitro secondary amine having the formula:

wherein A is a lower alkylene radical and R is a radical selected from the group consisting of lower alkyl and nitro radicals.

7. The method of preparing a N-nitroalkyl-L3-diazine, having the formula:

N05 1120 CHn N02 NO:(|3--A-N 1 I-A----0 N0a No, OH; NO: which comprises condensing formaldehyde with an amine wherein A is a lower alkylene radical.

8. The method of preparing a N-nitroalkyl-1,3-diazine, having the formula:

0 with formaldehyde.

References Cited in the file of this patent UNITED STATES PATENTS 2,391,847 'Senkus Dec. 25, 1945 

1. AS COMPOSITIONS OF MATTER, THE N-NITROALKYL-1,3DIAZINES HAVING THE FORMULA: 